EP3083549B1 - Procédé de fabrication d'esters non saturés à partir d'aldéhydes par estérisation oxydative directe - Google Patents

Procédé de fabrication d'esters non saturés à partir d'aldéhydes par estérisation oxydative directe Download PDF

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Publication number
EP3083549B1
EP3083549B1 EP14809815.5A EP14809815A EP3083549B1 EP 3083549 B1 EP3083549 B1 EP 3083549B1 EP 14809815 A EP14809815 A EP 14809815A EP 3083549 B1 EP3083549 B1 EP 3083549B1
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reactor
process according
liquid phase
catalyst
methacrolein
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German (de)
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EP3083549A1 (fr
Inventor
Steffen Krill
Alexander Lygin
Torsten Balduf
Rudolf Burghardt
Andreas Tepperis
Matthias Grömping
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Roehm GmbH Darmstadt
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Evonik Roehm GmbH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • B01J35/19—
    • B01J35/23—
    • B01J35/40—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/48—Silver or gold
    • C07C2523/52—Gold
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • C07C67/42—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of secondary alcohols or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a process for the preparation of methyl methacrylate by direct oxidative esterification of methacrolein.
  • Methyl methacrylate is used in large quantities for the preparation of polymers and copolymers with other polymerizable compounds. Furthermore, methyl methacrylate is an important building block for various, on methacrylic acid (MAS) based special esters, which can be prepared by transesterification with the corresponding alcohol.
  • MAS methacrylic acid
  • methyl methacrylate is predominantly produced starting from hydrocyanic acid and acetone via the resulting acetone cyanohydrin (ACH) as the central intermediate.
  • ACH acetone cyanohydrin
  • This method has the disadvantage that very large amounts of ammonium sulfate are obtained, the preparation of which is associated with very high costs.
  • Other methods using a raw material basis other than ACH are described in the relevant patent literature and have now been implemented on a production scale.
  • C-4 based raw materials such as isobutylene or tert-butanol are also used as starting materials, which are converted into the desired methacrylic acid derivatives via several process stages.
  • isobutylene or tert-butanol is generally oxidized to methacrolein in a first stage, which is then reacted with methacrylic acid with oxygen. The resulting methacrylic acid is subsequently converted into MMA with methanol. Further details of this procedure are, inter alia, in Ullmann's Encyclopedia of Industrial Chemistry 2012, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim , Methacrylic Acid and Derivatives, DOI: 10.1002 / 14356007.a16_441.pub2.
  • MMA is obtained by oxidation of isobutylene or tert-butanol with atmospheric oxygen in the gas phase on the heterogeneous contact to methacrolein and subsequent oxidative esterification reaction of methacrolein using methanol.
  • This process developed by ASAHI is among others in the documents US 5,969,178 and US 7,012,039 described. Disadvantage of this method is in particular a very high energy requirement.
  • palladium (lead) catalysts have the disadvantage that in a continuous operation leads to high losses of the lead component (so-called leaching). On the one hand, this leads to a complex wastewater disposal, on the other hand, lead salts must be continuously fed to the system.
  • EP 2 177 267 and EP 2 210 664 describe nickel oxide catalysts with a gold content between 1 and 80 mol%, which are presented on a support material, for the oxidative esterification of aldehydes to esters. These catalysts are used with a diameter between 10 and 200 microns. In particular, these particles are present with a shell structure in which the nickel oxide on the Surface and the gold is located on an inner layer. These catalysts lead at best to an MMA selectivity of up to 97.1% with a space-time yield of 9.6 mol MMA / h * kg catalyst.
  • EP 2 210 664 discloses a special variant in which catalyst particles in the nanometer range are applied to a support particle with a diameter between 10 and 200 microns. In one variant, this support particle has a size of 3 mm.
  • the catalyst may also be presented in a cylindrical or honeycomb form in a fixed bed reactor. Furthermore, the process control in such a reactor variant is not described.
  • EP 1 393 800 For example, gold particles or gold-containing particles with a diameter of less than 6 nm are described on a support material, in particular on a metal oxide, as a catalyst. Selectivity to MMA of up to 93% and space-time yields of up to 50.7 mol MMA / h * kg of catalyst at a gold content of the catalyst particles of 4.5 mol%.
  • the disclosure content of the EP 2 210 664 analogous.
  • the catalyst applied on a carrier is used in the form of a suspension catalyst.
  • a powdered catalyst is stirred as a solid in an appropriate reactor type, eg a slurry-type reactor, and contacted with the educts (in this case the aldehyde, the alcohol and an oxygen-containing gas), the mixture being mechanically is circulated and the catalyst is exposed to more or less great mechanical stress.
  • the mixing with the reactants is very good, it also leads to a discharge of amounts of catalyst or catalyst abrasion and thus to a faster consumption of the catalyst.
  • Methacrylic acid forms as a by-product of the MAL synthesis and the pH of the reaction mixture drops accordingly. This leads to further problems.
  • the by-product 1,1-dimethoxyisobutene (DMI) is formed as the acetal from methacrolein and methanol.
  • DMI 1,1-dimethoxyisobutene
  • a part of the methacrolein in the form of a dimethyl acetal is no longer available for further conversion to MMA, and the space-time yield of the MMA synthesis decreases accordingly.
  • the dimethylacetal also causes problems in the subsequent distillative workup of the MMA.
  • a mixture with too low a pH value has a negative effect on the stability and service life of the catalyst used (leaching, changing the pore structure of the catalyst, etc.).
  • the JP 2003048863 in that a basic solution for balancing the pH can be added.
  • This basic solution for example in the form of a NaOH solution, itself generally has a pH greater than 10.
  • slurry-type reactors used according to the prior art especially for the oxidative esterification is one or more reactors connected in cascade, which are circulated with a stirrer.
  • the addition of the base can be controlled to maintain a constant pH.
  • the boiler reactor is cooled by a heat exchanger to remove the exotherm of the reaction.
  • Homogeneous heat distribution in the reactor and on the surface of the catalyst - especially in the absence of so-called "hot spots" - is very important for achieving high selectivities and optimal utilization of the catalyst.
  • Gaseous oxygen must be used as a reagent to the system be fed continuously. Owing to the risk of explosion, oxygen must additionally be diluted with an inert gas, such as nitrogen. This in turn results in a large gas flow which must be brought into contact with the catalyst surface simultaneously with the liquid. Lower thermal conductivity of gases compared to liquids results in poorer heat distribution.
  • methods of the prior art are to be improved such that less 1,1-dimethoxyisobutene, less Michael adduct, and less methacrylic acid are formed in the free form during the oxidative esterification of methacrolein.
  • 1,1-dimethoxyisobutene is formed in an excessively acidic medium, while the Michael adduct is formed in a rather too basic medium as a by-product.
  • the method should be inexpensive compared to the prior art, in particular without major catalyst losses by abrasion or discharge feasible.
  • the method should be able to be carried out with relatively simple and inexpensive systems.
  • the plants should accordingly be associated with low investment costs.
  • the facilities should be easy to maintain, cause low maintenance costs and be safe to operate.
  • the objects are achieved by a novel process for the preparation of methyl methacrylate from methacrolein in a continuous oxidative esterification reaction with oxygen and methanol.
  • this process is carried out in the liquid phase at a pressure of 2 to 100 bar with a heterogeneous catalyst.
  • the heterogeneous catalyst is supported gold-containing nanoparticles having a particle size of less than 20 nm, preferably between 0.2 and 20 nm.
  • the inventive method is characterized in that the liquid phase is removed from the reactor continuously and the pH after the removal by adding a basic solution to a pH value between 5 and 9, preferably between 6 and 8.5 and more preferably between 6.5 and 8.0 is set. This withdrawn liquid phase having a pH of between 5 and 9 is then fed back into the reactor to at least 50%, preferably to at least 70% and particularly preferably to at least 90%.
  • the removal of the liquid phase can be carried out continuously, semicontinuously or batchwise, preferably continuously.
  • the reactor is a fixed bed reactor in which the gold-containing nanoparticles are on carrier particles having a total diameter between 0.2 and 20 mm, which in turn are presented in a fixed bed.
  • the catalyst is immobilized and there is usually a flow through the reactor with the reaction solution from bottom to top or vice versa.
  • no stirrer is needed for a fixed bed reactor.
  • Adjusting the pH by adding a basic solution directly to the reactor, as described in the prior art for stirred reactors, is negative for the catalyst life and selectivity of the reaction in a fixed bed reactor due to the lower mixing of the basic solution with the reaction solution , There are local differences in the pH, especially near the point of introduction of the basic solution.
  • the gold-containing nanoparticles are on carrier particles with an overall diameter of less than 0.2 mm.
  • the reaction is carried out in a stirred reactor, ie a reactor with stirring device.
  • the catalyst particles are circulated accordingly in the reaction solution.
  • the gold-containing nanoparticles are also on carrier particles with a total diameter less than 0.2 mm.
  • the reaction is carried out in a fluidized bed type apparatus.
  • the catalyst particles are circulated and distributed accordingly in a catalyst bed with a flowing liquid stream.
  • the oxidative esterification reaction is carried out at a pressure in the range of 2 to 50 bar and a temperature in the range of 10 to 200 ° C. It is particularly advantageous to carry out the reaction at a higher pressure than described in the prior art. For the workup, an increased reaction pressure is advantageous since surprisingly less cooling energy is required. Furthermore, the workup at elevated pressures is much easier and you can significantly reduce material losses. These effects can be explained by the fact that methyl methacrylate (MMA), methacrolein (MAL), methanol and the by-product methyl formate are low-boiling components.
  • the gaseous and the liquid reactants are fed simultaneously, preferably in the upper part of the reactor in the sense of a trickle bed reactor. Thus one achieves a very close, homogeneous distribution of gas and liquid, which in turn causes a high selectivity and constant activity of the catalyst.
  • Separation of the remaining gas phase may then be carried out, for example, prior to recycling the liquid phase to the reactor, e.g. directly in front of the container for pH adjustment, by means of the phase separator.
  • the oxidative esterification reaction is preferably carried out with a freshly fed into the reactor mixture of methanol and methacrolein, which is a proportion of the methacrolein based on the mixture in the range between 20 and 60% by weight, preferably between 25 and 40% by weight.
  • the remaining portion of the liquid phase is worked up to isolate the recovered MMA fed.
  • liquid phase is recycled 100% back to the reactor.
  • liquid phase is removed continuously, semicontinuously or batchwise at a different point of the reactor-and not in the circulation loop.
  • the methacrolein fed to the reactor from a preliminary stage or a storage vessel can be dehydrated by distillation before it is fed into the reactor, preferably in the presence of methanol.
  • the thus dewatered MAL and methanol-containing mixture can then be passed into the reactor.
  • this methacrolein may also be passed directly into the described distillation apparatus for dewatering the liquid phase withdrawn from the reactor. In this way, a distillation apparatus for dehydration of both phases is sufficient.
  • the oxygen concentration in the exhaust gas from the system is less than 8% by volume.
  • This can be done by an appropriate scheme of the oxygen content in the gas mixture fed to the oxidative esterification.
  • air with a further inert gas in the reaction such as nitrogen, carbon dioxide or argon, are diluted before the feed line.
  • Gas mixtures of such gases and pure oxygen can also be provided.
  • the oxygen content of the exhaust gas is preferably determined continuously by means of a probe, and the gas composition and / or gas quantity in the supply air are regulated automatically accordingly.
  • this fixed bed reactor with a catalyst bed volume / reactor volume ratio of greater than 0.01, preferably 0.1 and particularly preferably greater than 0.2.
  • FIG. 1 A possible embodiment of the invention with a fixed bed reactor is in Fig. 1 displayed.
  • Oxygen or O 2 -containing gas is fed via line 1 and a methacrolein / methanol solution via line 2 to the reactor A.
  • the components are mixed and the resulting heterogeneous gaseous / liquid mixture is further supplied via line 3 to the outer jacket temperable fixed bed reactor A.
  • both the gas / liquid mixture and the individual component can be supplied to the reactor from above as well as from below.
  • the reactor is filled with the corresponding fixed-bed catalyst, wherein the size of the individual catalyst particles must be large enough (D> 0.2 mm) to avoid pressure build-up in the reactor.
  • the catalyst particles should not exceed an optimal maximum size (D ⁇ 20 mm) in order to increase the contact surface between the catalyst and the reaction mixture.
  • the shell catalysts are preferably used in which the active components are preferably distributed on the surface.
  • the reaction mixture is cooled by means of a heat exchanger B and further fed to the phase separator (gas / liquid separation vessel) C.
  • the phase separator gas / liquid separation vessel
  • the exhaust gas can either be disposed of or preferably recycled.
  • the liquid phase is achieved via line 6 in the container D, in which pH is adjusted by adding an alkaline solution (eg, sodium hydroxide in methanol) via line 7 to a pH value between 5 and 9. A portion of this mixture is separated as a product via line 9, while the remainder is passed via line 8 back into the reactor A.
  • an alkaline solution eg, sodium hydroxide in methanol
  • not the complete reaction mixture is cooled by means of a heat exchanger (B) to the reactor, but only a part thereof, which is not returned to the reactor.
  • the heat exchanger B is omitted
  • most of the reaction mixture is recycled at a reaction temperature and only a part of it is removed via a heat exchanger (E) as a product and cooled.
  • a fixed bed reactor instead of a fixed bed reactor, another, e.g. Stirred reactor can be used.
  • the catalyst particle size depends on the type of reactor.
  • a slurry-bed reactor e.g. a powder catalyst with particle size ⁇ 0.2 mm used.
  • Catalyst 1 (0.9% Au-1.1% NiO on SiO 2 -Al 2 O 3 -MgO, 1.16-2.36 mm sphere)
  • This neutralized mixture was fed at a flow rate of 20.9 g / h together with an O 2 / N 2 gas mixture (7 vol% O 2 ) at 11 bar via a line to a tubular reactor heated to 70 ° C outer jacket.
  • the O 2 / N 2 flow was adjusted so that the proportion of O 2 in the exhaust gas was 4% by volume.
  • the reactor contained 15 g of the catalyst 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Dispersion Chemistry (AREA)

Claims (13)

  1. Procédé pour la préparation de méthacrylate de méthyle à partir de méthacroléine dans une réaction d'estérification oxydante continue avec de l'oxygène et du méthanol, qui est réalisée en phase liquide à une pression de 2 à 100 bars avec un catalyseur hétérogène, pour lequel il s'agit de nanoparticules supportées contenant de l'or présentant une grosseur de particule inférieure à 20 nm, caractérisé en ce que la phase liquide est prélevée en continu du réacteur et le pH après le prélèvement est réglé par addition d'une solution basique en dehors du réacteur à une valeur de pH entre 5 et 9 et en ce que la phase liquide prélevée présentant une valeur de pH entre 5 et 9 est recyclée à raison d'au moins 50% dans le réacteur.
  2. Procédé selon la revendication 1, caractérisé en ce que la phase liquide prélevée présentant une valeur de pH entre 5 et 9 est recyclée à raison d'au moins 70% dans le réacteur.
  3. Procédé selon la revendication 1, caractérisé en ce que la phase liquide prélevée présentant une valeur de pH entre 5 et 9 est recyclée à raison d'au moins 90% dans le réacteur.
  4. Procédé selon la revendication 1, caractérisé en ce que les nanoparticules contenant de l'or se trouvent sur des particules support présentant un diamètre total entre 0,2 et 20 mm et en ce que le procédé est réalisé dans un réacteur à lit fixe.
  5. Procédé selon la revendication 1, caractérisé en ce que les nanoparticules contenant de l'or se trouvent sur des particules support présentant un diamètre total inférieur à 0,2 mm et en ce que le procédé est réalisé dans un réacteur équipé d'un dispositif d'agitation.
  6. Procédé selon au moins l'une quelconque des revendications 1 à 5, caractérisé en ce que la réaction d'estérification oxydante est réalisée à une pression dans la plage de 2 à 50 bars et à une température dans la plage de 10 à 200°C.
  7. Procédé selon au moins l'une quelconque des revendications 1 à 6, caractérisé en ce que le mélange fraîchement injecté de méthanol et de méthacroléine est guidé dans le réacteur à une proportion de méthacroléine, par rapport au mélange, dans la plage entre 20 et 60% en poids, de préférence entre 25 et 40% en poids.
  8. Procédé selon au moins l'une quelconque des revendications 1 à 7, caractérisé en ce que la proportion résiduelle de la phase liquide prélevée en continu du réacteur, qui n'est pas recyclée dans le réacteur, est déshydratée et le mélange réduit en eau, contenant de la méthacroléine et du méthanol, est ensuite recyclé dans le réacteur.
  9. Procédé selon au moins l'une quelconque des revendications 1 à 8, caractérisé en ce que la phase liquide est recyclée à raison de 100% dans le réacteur et en ce que de la phase liquide pour le traitement ultérieur est prélevée en continu, de manière semi-continue ou par lots en un autre endroit du réacteur.
  10. Procédé selon au moins l'une quelconque des revendications 1 à 9, caractérisé en ce que la concentration en oxygène dans l'effluent gazeux du système est inférieure à 8% en volume.
  11. Procédé selon au moins l'une quelconque des revendications 1 à 10, caractérisé en ce que la valeur du pH de la phase liquide prélevée du réacteur est réglée à une valeur entre 6 et 8,5, de préférence entre 6,5 et 8,0.
  12. Procédé selon au moins l'une quelconque des revendications 1 à 11, caractérisé en ce que la méthacroléine est déshydratée par distillation avant l'introduction dans le réacteur en présence de méthanol.
  13. Procédé selon au moins l'une quelconque des revendications 1 à 12, caractérisé en ce que le réacteur à lit fixe est exploité à un rapport volume de catalyseur/volume de réacteur supérieur à 0,2.
EP14809815.5A 2013-12-20 2014-12-05 Procédé de fabrication d'esters non saturés à partir d'aldéhydes par estérisation oxydative directe Active EP3083549B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14809815.5A EP3083549B1 (fr) 2013-12-20 2014-12-05 Procédé de fabrication d'esters non saturés à partir d'aldéhydes par estérisation oxydative directe

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13198863.6A EP2886528A1 (fr) 2013-12-20 2013-12-20 Procédé de fabrication d'esters non saturés à partir d'aldéhydes par estérisation oxydative directe
EP14809815.5A EP3083549B1 (fr) 2013-12-20 2014-12-05 Procédé de fabrication d'esters non saturés à partir d'aldéhydes par estérisation oxydative directe
PCT/EP2014/076682 WO2015091018A1 (fr) 2013-12-20 2014-12-05 Procédé de production de d'esters insaturés à partir d'aldéhydes par estérification oxydative directe

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EP3083549A1 EP3083549A1 (fr) 2016-10-26
EP3083549B1 true EP3083549B1 (fr) 2017-09-20

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EP13198863.6A Withdrawn EP2886528A1 (fr) 2013-12-20 2013-12-20 Procédé de fabrication d'esters non saturés à partir d'aldéhydes par estérisation oxydative directe
EP14809815.5A Active EP3083549B1 (fr) 2013-12-20 2014-12-05 Procédé de fabrication d'esters non saturés à partir d'aldéhydes par estérisation oxydative directe

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EP13198863.6A Withdrawn EP2886528A1 (fr) 2013-12-20 2013-12-20 Procédé de fabrication d'esters non saturés à partir d'aldéhydes par estérisation oxydative directe

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US (1) US9617199B2 (fr)
EP (2) EP2886528A1 (fr)
JP (1) JP6479017B2 (fr)
KR (1) KR102336765B1 (fr)
CN (1) CN105722816B (fr)
BR (1) BR112016014331A2 (fr)
ES (1) ES2647148T3 (fr)
MY (1) MY171922A (fr)
RU (1) RU2643369C2 (fr)
SA (1) SA516371327B1 (fr)
SG (1) SG11201602583PA (fr)
TW (1) TWI651298B (fr)
WO (1) WO2015091018A1 (fr)

Families Citing this family (38)

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Publication number Priority date Publication date Assignee Title
EP3170558A1 (fr) 2015-11-19 2017-05-24 Evonik Röhm GmbH Catalyseur pour l'esterification oxydative d'aldehydes en esters d'acide carbonique
EP3235560A1 (fr) 2016-04-22 2017-10-25 Evonik Röhm GmbH Procede d'execution d'une reaction sous catalyse heterogene
KR102619749B1 (ko) * 2017-05-09 2023-12-29 룀 게엠베하 알데히드의 카르복실산 에스테르로의 산화 에스테르화 방법
CN111051274A (zh) * 2017-07-28 2020-04-21 陶氏环球技术有限责任公司 通过使用非均相催化剂进行氧化酯化来生产甲基丙烯酸甲酯的方法
SG11202000694WA (en) 2017-07-28 2020-02-27 Rohm & Haas A method for production of methyl methacrylate by oxidative esterification using a heterogeneous catalyst
EP3658529A1 (fr) 2017-07-28 2020-06-03 Rohm and Haas Company Procédé de production de méthacrylate de méthyle par estérification oxydative à l'aide d'un catalyseur hétérogène
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EP3083549A1 (fr) 2016-10-26
US20160251301A1 (en) 2016-09-01
TWI651298B (zh) 2019-02-21
US9617199B2 (en) 2017-04-11
BR112016014331A2 (pt) 2017-10-31
MY171922A (en) 2019-11-07
WO2015091018A1 (fr) 2015-06-25
JP6479017B2 (ja) 2019-03-06
CN105722816B (zh) 2018-01-23
SG11201602583PA (en) 2016-05-30
CN105722816A (zh) 2016-06-29
JP2017504607A (ja) 2017-02-09
RU2643369C2 (ru) 2018-02-01
KR20160102498A (ko) 2016-08-30
EP2886528A1 (fr) 2015-06-24
TW201536738A (zh) 2015-10-01
KR102336765B1 (ko) 2021-12-07
SA516371327B1 (ar) 2019-01-16
RU2016129243A (ru) 2018-01-25
ES2647148T3 (es) 2017-12-19

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